Basic dyes of the naphtholactam series

ABSTRACT

BASIC DYES HAVING THE FORMULA I:   1-(NC-CH2-CH2-),2-(2-R,4-(R1-N(-R2)-)PHENYL)BENZ(CD)-   INDOLIUM A(-)   WHERE R IS HYDROGEN, CHLORINE, METHYL, METHOXY, ETHOXY, ACETYLLAMINO OR PROPIONYLAMINO, R1 IS UNSATURATED OR SUBSTITUTED ALKYL, ARALKYL OR ARYL, R2 IS HYDROGEN OR UNSUBSTITUTED OR SUBSTITUTED ALKYL OR ARALKYL R1 AND R2 TOGETHER WITH THE NITROGEN DENOTE THE RADICAL OF A HETEROCYCLIC RING AND A$ IS AN ANION, THE NAPHTHALENE RINGS A IF DESIRED BEARING CHLORINE, BROMINE, OR UNSUBSTITUTED OR SUBSTITUTED SULFONAMIDE GROUPS AS SUBSTITUENTS.

United States Patent Office 3,801,596 Patented Apr. 2, 1974 US. Cl. 260-32662 4 Claims ABSTRACT OF THE DISCLOSURE Basic dyes having the Formula I:

where R is hydrogen, chlorine, methyl, methoxy, ethoxy, acetylamino or propionylamino, R is unsubstituted or substituted alkyl, aralkyl or aryl, R is hydrogen or unsubstituted or substituted alkyl or aralkyl R and R together with the nitrogen denote the radical of a heterocyclic ring and A is an anion, the naphthalene rings A if desired bearing chlorine, bromine or unsubstituted or substituted sulfonamide groups as substituents.

The present invention relates to the basic dyes of Formula I above. As suitable substituents, examples of substituents R are methyl, ethyl, propyl, butyl, fl-hydroxyethyl, B-cyanoethyl, fi-chloroethyl, benzyl, phenylethyl, phenyl, ethoxyphenyl and methoxyphenyl, R may be for example methyl, ethyl, propyl, butyl, B-hydroxyethyl and fi-cyanoethyl.

Those dyes are of particular industrial interest which have the general formula where R is alkyl having 1 to 4 carbon atoms, ,8-hydroxyethyl, p-cyanoethyl, B-chloroethyl, benzyl, fl-phenylethyl, phenyl or ethoxyphenyl, R is alkyl having 1 to 4 carbon atoms, ,B-hydroxyethyl, p-cyanoethyl, fl-chloroethyl or hydrogen, Y is hydrogen, chlorine, bromine or a N,N-disubstituted sulfonamide group, and A is an anion.

Substituted sulfonamide groups Y are for example N,N- dimethylsulfonamide, N,N diethylsulfonarnide, N,N dibutylsulfonamide, or the groups which may be identified as morpholino sulfonyl, piperidino sulfonyl and pyrrolidino sulfonyl.

Anions A include the chloride, bromide, nitrate, sulfate, methosulfate, ethosulfate, benzene sulfonate, toluene sulfonate, formate, acetate, tetrafiuoborate and tetrachlorozincate.

For the production of dyes of Formula I, naphtholactams having the General Formula II:

may be reacted with amines having the General Formula III:

cyanoethyDnaphtholactam, 6-bromo N (B-cyanoethyl) naphtholactam, and N 3 cyanoethyl)naphtholactam-6- sulfonic acid diethylamide, dimethylamide, pyrrolidide, morpholide or piperidide. They may be obtained by the reaction of acrylonitrile with naphtholactam or naphtholactam derivatives in the presence of basic condensing agents. Introduction of any substituents (chlorine, bromine, sulfonamide) may be effected before or after the reaction with acrylonitrile.

Basic condensing agents for introducing the radical CH CH CN are for example sodium methoxide, sodium ethoxide and trimethylbenzyl ammonium hydroxide.

Examples for components of Formula III are N,N-dialkylanilines, N,N-dialkyl m tolnidines, diphenylamine and N-alkyldiphenylamines that may bear alkyl, acylamino or alkoxy radicals as substituents in the aryl radical. Specific compounds are dimethylaniline, dibutylaniline, dimethyl-m-toluidine, diethyl-m-toluidine, dibutylm-toluidine, diethyl-m-chloroaniline, N-p-cyanoethyl-N- bntylaniline, N-,B-hydroxyethyl-N-ethylaniline, 3-diethylaminoacetanilide, N fi-acetoxyethyl-N-ethyl-m-toluidine, N-phenylmorpholine, N-ethyldiphenylamine, N-methyl-4- ethoxydiphenylamine, N a cyanoethyl-N-methylaniline and N-a-cyanoethyl-N-ethylaniline.

The dyes of Formula I are suitable for dyeing tannintreated cotton, leather, paper, or inks for ball point pens, and particularly for dyeing and for printing textiles or other materials of anionically modified polyesters and acrylonitrile polymers.

The water-soluble blue to greenish blue dyes give deep blue colorations very fast to light and wet treatments on textile materials of acrylonitrile polymers. As compared with comparable known dyes, the new dyes having an N- methyl or N-ethyl naphtholactam component exhibit a tinctorially valuable bathochromic shift from blue violet toward blue and many of them also have improved lightfastness. Moreover, the dyes of the invention are distinguished by a neutral shade in artificial light.

The invention is further illustrated by the following examples in which parts and percentages are by weight unless otherwise specified.

EXAMPLE 1 22.2 parts of N-fl-cyanoethyl-peri-naphtholactam, 8 parts of zinc chloride and 60 parts of phosphorus oxychloride are heated at 110 C. for 30 minutes.

Then a solution of 18 parts of diethylaniline in 70 parts of ethylene chloride is slowly added. The whole is heated for three hours at 80 C., the reaction mixture poured into water and the ethylene chlorine distilled olf.

The crystalline dye of the formula ZnCh which precipitated dyes acrylonitrile polymers fast blue shades.

EXAMPLE 2 22 parts of N-B-cyanoethyl-peri-naphtholactam and 85 parts of phosphorus oxychloride are heated at 110 C. for 40 minutes. Then 15 parts of dimethylaniline is added and the temperature kept at 95 C. for five hours. The mixture is poured into ice water and neutralized with sodium acetate solution. The resultant blue dye has the formula EXAMPLE 3 30.1 parts of 6-bromo-N-(fi-cyanoethyl)-peri-naphtholactam, 150 parts of phosphorus oxychloride and 10 parts of zinc chloride are kept at 115 C. for one hour with stirring. 24 parts of N-fl-cyanoethyl-N-butylaniline is slowly added and the whole heated for four hours under reflux. The mixture is then poured onto ice to yield the blue dye of the formula in a good yield.

EXAMPLE 4 22 parts of N-(fi-cyanoethyl)-peri-naphtholactam, 80

EXAMPLE 5 37 parts of N-(/S-cyanoethyl)-peri-naphtholactam-6-sulfonic acid morpholide, 75 parts of phosphorus oxychloride and 10 parts of zinc chloride are added together and the mixture is kept at 115 C. for 40 minutes. Then a solution of 18 parts of N-phenylmorpholine in parts of chloroform is slowly added and the whole heated for four hours under reflux. The reaction mixture is poured into hot water and the chloroform removed by distillation. Upon cooling, the dye of the formula SOa-N H b precipitates in crystalline form. It dyes polyacrylonitrile fibers fast blue shades.

EXAMPLE 6 32.9 parts of N-(fl-cyanoethyl)-peri-naphtholactam-6- sulfodimethylamide, 75 parts of phosphorus oxychloride and 8 parts of zinc chloride are kept at C. for 30 minutes with stirring. 27.5 parts of N-5-phenylethyl-N-ficyanoethylaniline is added and the whole heated under reflux for four hours. By pouring the mixture into ice water and neutralizing the strongly acid solution the blue dye of the formula is obtained in a good yield.

are obtained that dye acrylonitrile polymers in the shades indicated:

i sg szs rsu- Ex. Naphtholactam B beinggig e 1 NC-C;H41}I--(1=0 CH1 Blue.

m fin CH; Blue violet.-

C:H4CN

11 do C Hg Blue.

CzH4CN CaH4OH do CHHOH Violet.

C:H OH

14 (In em, Blue.

15 do N/CzH; Reddlsh blue.-

C2H4CN 16 fin C1H4GN Blue;

17 an Do;

1;: do NQ Do.-

10 do CzHaCN Violet.

20 r10 0 H; Do.-

21 an 0H; Do;

@R Shade of dyeing on aerylonitrile Ex; Naphtholactam R beingpolymer 52....-. Same as Example 50 /O:H| Blue.

53..... NC-C:H4N-C=0 Q Blulsh green.

N-- 01H; H

54...-.. NC--C:Hr-N-O=O CHI Blue;

55...; Same as above....nacinnnzus; (32H! D0.

56 do 01H] D0.

ciHicN 57 do CtHn D0.

C1HCN We claim: morpholino, pyrrolidino, piperidino, piperazino or N- 1. A compound of the formula methylpiperazino,

Cm X denotes hydrogen, chlorine, bromine, sulfonamide which is N-substituted by lower alkyl, pyrrolidino sulfonyl, NCHCPN'C 40 piperidino sulfonyl or morpholino sulfonyl,

0=H| Z denotes hydrogen, chlorine or bromine and 9 A denotes an anion.

4. A compound of the formula e ('11 NC CHzCHs-N=C N A wherein A is an anion. RG

2. A compound of the formula 9 NC-C:HN=C N\ 0,11. Y 6 where:

R denotes alkyl of l to 4 carbon atoms, fi-hydroxyethyl, p-cyanoethyl, B-chloroethyl, benzyl, p-phenylethyl, phen. wherein A is an anion. yl or ethoxyphenyl,

3. A compound of the formula R denotes hydrogen, alkyl of 1 to 4 carbon atoms, 18-

hydroxyethyl, B-cyanoethyl or p-chloroethyl, 6B e R and R when taken together with the nitrogen form NCCHCHPIII=C' A morpholino, pyrrolidino, piperidino, piperazino or N- R R methylpiperazino, x z Y denotes hydrogen, chlorine, bromine, sulfonamide N- substituted by lower alkyl, pyrrolidino sulfonyl, piperidino sulfonyl or morpholino sulfonyl, and

where:

A denotes an anion.

No references cited.

NICHOLAS S. RIZZO, Primary Examiner I. TOVAR, Assistant Examiner US. Cl. X.R.

260-242, 247.1, 247.5, 247.2 R, 268 TR, 270 R, 293.61, 326.3; 8177 AB UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,801,595 DATED April 2, 1974 v (g BAUMANN et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Column 1, Line 29, after the word "aralkyl" insert In Column 4, Line 9-21 (Formula of example 4), delete ll 6 II I C-C2H4-N c -E- -OC2H5 l/2 ZnCl 2 r substitute G9 NC-C2H4-N c filo-Q OC2H5 1/2 ZnCl 2 Signed and Scaled this Thirteenth Day of July 1976 [SEAL] Attest:

RUTH C. MASON ANesting Officer 

